CN1490058A - Preparing method for biological active peptide and titanium alloy hard tissue implanting material - Google Patents
Preparing method for biological active peptide and titanium alloy hard tissue implanting material Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 18
- 108090000765 processed proteins & peptides Proteins 0.000 title 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 33
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- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002513 implantation Methods 0.000 abstract description 2
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Abstract
A bioactive Ti or Ti alloy used as the hard tissue implantation material is prepared from Ti or Ti alloy through electrochemical treating to generate an oxidized film on surface, chemical treating with alkali solution to generate a porous reticular layer of titanate gel, heat treating to make said gel layer become crystalline, and immersing in human bionic liquid to generate phoshpotite layer. Its advantages are high hardness and binding strength to basic body, and low cost.
Description
Technical Field
The invention relates to the field of preparation of bioactive implant materials, in particular to a preparation method of a bioactive titanium and titanium alloy hard tissue implant material.
Background
The progress of modern scientific technology has enabled mankind to reform and create new life forms, and the artificial organization of organs has become one of the top technologies of today's medical science. The potential core of the method is the development of medical biomaterials, the development of the medical biomaterials can lead people to remove tissues and replace the tissues to finally realize tissue reconstruction, the Ti alloy has the advantages of high strength, low elastic modulus, good corrosion resistance and the like, and is always concerned by people in the research and application of artificial implants, but the titanium and the titanium alloy are biological inert metal materials and can not be directly and biologically combined with the tissues of the human body, so the research and application of preparing bioactive titanium and titanium alloy surface materials increasingly gains attention of medical circles of various countries.
In the prior art, a plasma spraying method is mostly adopted to prepare a Hydroxyapatite (HA) coating in the technology of modifying the surfaces of titanium and titanium alloy to enable the titanium and titanium alloy to have bioactivity, and the HA coating is easy to decompose due to the fact that plasma spraying is carried out at high temperature (12000 ℃), the residual stress between the coating and a matrix is high, the bonding strength between the coating and the matrix is poor, the coating is not compact, and biological body fluid is easy to permeate into the matrix to cause the defects of interface corrosion, implant loosening and the like.
The method for preparing various hydroxyapatite biological ceramic coatings is introduced in the No. 6 of the volume 14 of the Material development and application in the month 12 1999, and the advantages and the disadvantages of various methods are compared; the research on medical titanium and titanium alloy implants is introduced in the 3 rd month in 2000, volume 5, phase 1 of the journal of Chinese oral implantology, and the research progress of titanium and titanium alloy implant materials in recent years is reviewed from four aspects; the preparation of bioactive titanium and titanium alloy implant materials by chemical and electrochemical modification methods has not been reported.
Disclosure of Invention
The invention aims to provide a preparation method of a bioactive titanium and titanium alloy hard tissue implant material which has high bonding strength with a matrix and uniform film thickness and can effectively solve the problem of biological inertness of titanium and titanium alloy.
In order to achieve the purpose, the technical scheme of the invention is to prepare a bioactive film by self-growing on the surface of titanium and titanium alloy by adopting an electrochemical and chemical composite surface modification technology, wherein the film has high hardness, wear resistance and capability of preventing metal ions from releasing, and the specific method comprises the following steps:
1) adding 5-40 g/L nitrate or sulfate electrolyte into an alcohol organic solvent to prepare electrolyte, taking titanium or titanium alloy as an anode, taking titanium, titanium alloy, stainless steel, carbon, platinum or lead as a cathode, and taking the electrolyte as a conductive medium to carry out anodic oxidation, wherein the electrolysis parameters are as follows: the temperature of the electrolyte is 10-80 ℃, and the current density is 5-40 mA/cm2Anodizing for 20-120 min to form an oxide film with a thickness of 5-50 μm on the surface of titanium and titanium alloy, and controlling the components of the oxide film by a process to ensure that the oxide film does not contain harmful metals such as V and the like;
2) soaking the titanium oxide film in 1-20 mol/L aqueous alkali at 30-80 ℃ for 5-48 hours to form a porous titanate gel layer with a net structure on the surface of the oxide film;
3) carrying out heat treatment on the materials at the temperature of 400-900 ℃ for 0.5-3 hours, heating along with a furnace, and cooling along with the furnace to crystallize a titanate gel layer with a net structure, wherein the thickness of the titanate gel layer is 5-20 mu m;
4) the treated material is immersed in the human body bionic liquid for 1-30 days to form a Ca and P rich apatite layer which is similar to bone, the prepared implant material has high hardness and wear resistance, can prevent harmful ions in a matrix from being released, and the film has high bonding strength with the matrix and uniform thickness.
The metal Ti generally has two crystal forms, one is α -Ti and is a close-packed hexagonal crystal system, and the other is β -Ti and is a body-centered cubic crystal system, the transformation temperature of the metal Ti is 882.5 ℃, and the metal Ti has two crystal forms, namely, a first crystal form, a second crystal form, a third crystal form and a fourth crystal form, wherein the first crystal form is a close- The standard electrode potential of (v) (-) -1.63v (she) shows that Ti is a very active metal. Ti generally exhibits excellent corrosion resistance because Ti is highly likely to react with oxygen in the air or other oxidizing agents to form oxide films of various valence states on the surface (Ti)2O3And TiO2α -Ti can absorb 14.5% (at) of oxygen to form a solid solution at normal temperature, and in most media, the passivation potential Ep of Ti is lower than the standard electrode potential of hydrogen, which is a characteristic property of Ti and chromium2SO4Etc.) in the presence of dissolved oxygen or other oxidizing agents, or in the presence of heavy metal ions such as Fe3+、Cu2+、Al3+、Pt4+And the like, all of which can passivate Ti. Besides acids such as HF, which have strong solubility in Ti matrix, Ti can be almost oxidized in other electrolyte aqueous solutions. It is worth noting that the presence of water in the medium plays an important role in the formation of oxide films and the performance of the films. The tendency of Ti to passivate in the wet state is greater than that in the dry state, in particular the influence of water in organic solvents on the passivating behavior of TiMore significantly, it can be seen that in non-aqueous or less aqueous solutions, Ti hardly exhibits its inertness. From the above oxidation characteristics, titanium and titanium alloys are easily provided with various oxide films in an aqueous solution containing an oxidizing substance.
When the sample is treated by alkali solution, a porous network structure is formed on the surface, and the network structure layer is a titanate gel layer which is TiO on the surface of Ti alloy2The film is corroded by alkali liquor and partially dissolved to generate a series of products of chemical reactions. During the alkali treatment, when the concentration of the alkali solution is increased, the net-shaped structure layerThe pore size also increases, but when the alkali concentration reaches more than 20mol/L, the network structure of the titanate gel layer does not change greatly. Therefore, when the concentration of the alkali liquor is 1-20 mol/L, a uniform sodium titanate gel layer is formed on the surface of the Ti alloy. After heat treatment, the sodium titanate gel layer on the surface can be dehydrated to form an amorphous or crystalline titanate layer. And with the continuous increase of the heat treatment temperature, the sodium titanate gel layer is gradually crystallized and becomes more and more compact. The oxide film on the surface of the titanium and the titanium alloy after the anodic oxidation treatment is immersed into the human body bionic solution SBF to form a Ca and P rich apatite layer which is similar to bone substance after the alkali treatment and the heat treatment process.
The invention has the following beneficial effects:
1. the invention adopts electrochemical and chemical composite surface modification technology to self-grow a bioactive film on the surface of titanium and titanium alloy, and prepares a thick oxide film on the surface of titanium and titanium alloy by an electrochemical method, aiming at forming a layer of protective film on the surface of Ti or Ti alloy, so that the release of harmful metal ions is prevented, the wear resistance of the material is improved, the thickness of the film is uniform, the hardness is high, the bonding strength with a substrate is high, and the problems of biological inertia, metal ion release and the like existing in the current titanium and titanium alloy biological implantation material can be effectively solved.
2. The invention adopts the microcrystal oxidation film with bioactivity which grows on the surface of the titanium and titanium alloy implant material prepared by the electrochemistry and chemical composite surface technology, the film can generate a apatite layer which is rich in Ca and P and has similar bone components in the bionic liquid of a human body, and can form biological combination with hard tissues of the organism, the titanium and titanium alloy play a strong role of a bracket for the film layer and effectively serve as a bracket for new bone formation, and the self-growing bioactive film has good biocompatibility and finally forms a whole with bone tissues, thereby being an ideal artificial synthetic bone implant material.
3. The invention has simple manufacturing technology and lower cost, can be widely applied to replacement of bones and joints and repair and replacement materials of teeth, and can even be applied to vertebroplasty or artificial vertebroplasty clinic of extremity segmental bone defect caused by trauma and tumor, spinal tuberculous bone defect, osteolytic metastasis, myeloma and spinal angioma.
Drawings
FIGS. 1(a) and (b) are sectional views of titanium oxide films in examples 1 and 2 under different anodizing conditions, respectively.
FIG. 2 is an Auger electron spectroscopy analysis of constituent elements of the titanium oxide film of FIG. 1 (a).
FIG. 3 is an X-ray energy spectrum analysis of the composition of the titanium oxide film in FIG. 1 (a).
FIG. 4 is the SEM morphology of example 1 after anodization and treatment with a 10mol/L NaOH solution.
FIG. 5 is the SEM topography of example 1 at a heat treatment temperature of 800 ℃.
FIG. 6 shows the SEM appearance of the sample of example 1 after 10 days of soaking in SBF.
FIG. 7 is an X-ray energyspectrum of the apatite component of surface bone in example 1.
FIG. 8 is the SEM morphology of example 3 after anodization and treatment with a 5mol/L NaOH solution.
FIG. 9 is the SEM topography of example 3 at a heat treatment temperature of 600 ℃.
FIG. 10 shows the SEM image of example 3 after 5 days of soaking in SBF.
Detailed Description
Example 1
The surface of the Ti6Al4V alloy is treated by the method of the invention, which comprises the following steps:
1) ti6Al4V alloy is selected, and the sample size is 25 multiplied by 15 multiplied by 1mm3The sample is first passed through 400#Polishing the waterproof abrasive paper to generate a rough surface, then cleaning the rough surface for 5 times by using acetone in an ultrasonic cleaner, cleaning the rough surface by using distilled water, taking out the rough surface and drying the rough surface;
2) the preparation method of the electrolyte comprises the following steps: in 1L of methanolAdding 25g of analytical pure sodium nitrate chemical reagent into the solution (the water content is less than 1 percent) to prepare electrolyte, wherein the concentration of the electrolyte is 25g/L, Ti6Al4V alloy is used as an anode, a carbon rod is used as a cathode, the electrolyte is used as a conductive medium, and the anodic oxidation is carried out, and the electrolysis parameters are as follows: the temperature of the electrolyte is 50 ℃, and the current density is 25mA/cm2When the oxidation time is 80min, a uniform, compact and thick titanium oxide film is obtained, the thickness of the prepared oxide film can reach 35 mu m through the treatment, and the components of theoxide film are controlled by a process so as to be free of harmful metals such as V and the like;
3) soaking the sample subjected to anodic oxidation treatment in 10mol/L NaOH solution at 40 ℃ for 36h, and forming a porous titanate gel layer with a net structure on the surface of the oxidation film;
4) after being subjected to anodic oxidation treatment and being soaked in NaOH solution, a sample is subjected to heat treatment at the temperature of 800 ℃ for 2 hours, the temperature is increased along with the furnace, the sample is cooled along with the furnace, so that a titanate gel layer with a net structure is crystallized, and the thickness of the titanate gel layer is 12 microns; then placing the mixture in human body bionic liquid SBF, and after soaking for 10 days, forming a bone apatite layer on the surface of the mixture.
FIG. 1(a) shows the cross-sectional morphology of the oxide film formed in step 2), and the oxide film is tightly bonded to the substrate, and no cracking, peeling, etc. of the oxide film are observed.
FIG. 2 is an Auger electron spectroscopy analysis of the constituent elements of the oxide film. (a) Auger electron spectrum at the edge of the oxide film; (b) auger electron spectrum of the central part of the oxide film; (c) is the Auger electron energy spectrum of the interface of the oxide film and the matrix. The graph shows that the oxide film mainly comprises Ti and 0 element, the oxide film mainly comprises Ti oxide, the appearance of Al peak also shows that the oxide film also contains aluminum oxide, but no V peak appears in the whole graph, which shows that no vanadium oxide is formed in the oxide film, and the diffusion activation energy of V is small, and the V cannot diffuse outwards through the compact titanium oxide film, which shows that the oxide film has good barrier property and can prevent the release of metal V ions.
FIG. 3 is an EDX spectrum of X-ray energy spectrum point analysis of the oxide film composition. As can be seen from the graph, the composition of the oxide film is mainly Ti oxide. No V element is found except Ti, O, Al, C and N elements in the whole spectrum, and the result completely accords with the Auger electron spectrum analysis result of the experiment, which shows that the titanium oxide film prepared by the experiment has good barrier property and can effectively prevent the release of metal ions.
FIG. 4 shows the surface morphology of SEM after a sample is anodized and soaked in a 10mol/L NaOH solution at 40 ℃ for 36 h. As can be seen from the figure, after the sample is treated by the NaOH solution, a porous network structure is formed on the surface, and the network structure layer is sodium titanate (Na)2Ti5O11) And the gel layer is a product generated by a series of chemical reactions after the titanium oxide film on the surface of the Ti6Al4V alloy is corroded by alkali liquor and is partially dissolved.
FIG. 5 shows the surface morphology of SEM after the sample is anodized, soaked in 10mol/L NaOH solution at 40 ℃ for 36h, and then heat-treated at 800 ℃ for 2 h. As can be seen from the figure, when the titanium oxide film is treated with NaOH and heat, the sodium titanate gel layer on the surface of the titanium oxide film is dehydrated to form an amorphous or crystalline sodium titanate layer.
FIG. 6 shows SEM morphology of bone apatite formed on surface of sample after being anodized and treated with 10mol/LNaOH, then being heat treated at 800 deg.C for 2h, and then being placed in human body bionic solution SBF, and being soaked for 10 days. As can be seen from the figure, when the sample is treated with NaOH, spherical bone apatite is formed on the surface of the sample when the sample is soaked in SBF, which shows that the Ti alloy has bioactivity and the ability of bonding with bone tissues after proper anodic oxidation and NaOH treatment.
FIG. 7 is an X-ray energy spectrum analysis diagram of the elemental composition of bone apatite formed on the surface of a sample, and it can be seen from the diagram that the bone apatite formed on the surface of the sample is mainly composed of Ca and P elements, which is a kind of bone substance. No V element other than Ca, P, Ti, O, C and Al elements was present in the entire spectrum, consistent with the results of the experiment for preventing ion release of the oxidized Ti film by auger electron spectroscopy of fig. 2, indicating that the oxidized Ti film prepared by anodic oxidation did not release metal ions V from the Ti alloy matrix after the NaOH solution and heat treatment. This indicates that the titanium oxide film prepared by this experiment has good barrier properties. When soaked in SBF solution, bioactive bone apatite can be formed on the surface of the SBF after 10 days, which shows that the Ti6Al4V alloy has the capability of forming osseointegration with bone tissue after a series of processes such as electrochemistry, chemistry and heat treatment.
Example 2
The difference from the example 1 is that: ti6Al4V alloy is selected, and the sample size is 25 multiplied by 15 multiplied by 1mm3The sample is first passed through 400#Polishing the waterproof abrasive paper to generate a rough surface, then cleaning the rough surface for 4 times by using acetone in an ultrasonic cleaner, cleaning the rough surface by using distilled water, taking out the rough surface and drying the rough surface; the preparation method of the electrolyte comprises the following steps: adding 10g of analytically pure potassium sulfate chemical reagent into 1L of methanol solution (the water content is less than 1%) to prepare electrolyte, wherein the concentration of the electrolyte is 10g/L, Ti6Al4V alloy is used as an anode, a platinum sheet is used as a cathode, the electrolyte is used as a conductive medium, and the anodic oxidation is carried out, wherein the electrolysis parameters are as follows: the temperature of the electrolyte is 20 ℃, and the current density is 10mA/cm2When the oxidation time is 120min, a uniform, compact and thick titanium oxide film is obtained, and the thickness of the prepared titanium oxide film is 40 mu m after the treatment.
FIG. 1(b) shows the cross-sectional morphology of the oxide film formed, the oxide film is tightly bonded to the substrate, and no cracking, peeling, etc. of the oxide film are observed.
Example 3
The method is adopted to treat the surface of the metal Ti, and comprises the following steps:
1) selecting metal Ti, and the sample size is 20 multiplied by 10 multiplied by 1mm3The sample is first passed through 400#Polishing the waterproof abrasive paper to generate a rough surface, then cleaning for 3 times by using acetone in an ultrasonic cleaner, cleaning by using distilled water, taking out and drying;
2) the preparation method of the electrolyte comprises the following steps: adding 15g of analytically pure sodium nitrate chemical reagent into 1L of methanol solution to prepare electrolyte, wherein the concentration of the electrolyte is 15g/L, titanium is used as an anode, orThe steel is used as a cathode, the electrolyte is used as a conductive medium, anodic oxidation is carried out, and the electrolysis parameters are as follows: the temperature of the electrolyte is 60 ℃, and the current density is 15mA/cm2When the oxidation time is 90min, obtaining a uniform, compact and thick titanium oxide film, treating the titanium oxide film to obtain the oxidefilm with the thickness of 40 mu m, and controlling the components of the oxide film by a process so that the oxide film does not contain harmful metals such as V and the like;
3) soaking the sample subjected to anodic oxidation treatment in a 5mol/L NaOH solution at 60 ℃ for 18h to form a porous titanate gel layer with a net structure on the surface of the oxidation film;
4) after being subjected to anodic oxidation treatment and being soaked in NaOH solution, a sample is subjected to heat treatment at the temperature of 600 ℃, the heat preservation time is 1h, the temperature is increased along with a furnace, the temperature is cooled along with the furnace, so that a titanate gel layer with a net structure is crystallized, and the thickness of the titanate gel layer is 8 mu m; then placing the mixture in human body bionic liquid SBF, and after soaking for 5 days, forming a bone apatite layer on the surface of the mixture.
FIG. 8 shows the surface morphology of SEM after the sample is anodized and soaked in 5mol/L NaOH solution at 60 ℃ for 18 h. As can be seen from the figure, after the sample is treated by the NaOH solution, a layer of porous network structure is formed on the surface; the network structure layer is sodium titanate (Na)2Ti5O11) A gel layer of TiO on the surface of Ti2The film is corroded by alkali liquor and partially dissolved to generate a series of chemical reactions to generate products.
FIG. 9 shows the surface morphology of SEM after the sample is anodized, soaked in 5mol/L NaOH solution at 60 ℃ for 18h, and then heat-treated at 600 ℃ for 1 h. As can be seen from the figure, when the titanium oxide film is treated with NaOH and heat, the sodium titanate gel layer on the surface of the titanium oxide film is dehydrated to form an amorphous or crystalline sodium titanate layer.
FIG. 10 shows SEM morphology of bone apatite formed on the surface of a sample after the sample is subjected to anodic oxidation treatment and NaOH solution soaking, then is subjected to 600 ℃ heat treatment for 1h, is placed in human body bionic liquid SBF, and is soaked for 5 days. As can be seen, when the sample is treated, spherical bone apatite is formed on the surface of the sample after being soaked in SBF, which indicates that Ti has bioactivity after being properly anodized and treated with NaOH.
Claims (3)
1. A method for preparing bioactive titanium and titanium alloy hard tissue implant materials is characterized in that a method of electrochemical and chemical composite surface modification is adopted to prepare a bioactive film on the surface of titanium and titanium alloy through self-growth, and the specific method is as follows:
1) adding 5-40 g/L nitrate or sulfate electrolyte into an alcohol organic solvent to prepare electrolyte, taking titanium or titanium alloy as an anode, taking titanium, titanium alloy, stainless steel, carbon, platinum or lead as a cathode, and taking the electrolyte as a conductive medium to carry out anodic oxidation, wherein the electrolysis parameters are as follows: the temperature of the electrolyte is 10-80 ℃, and the current density is 5-40 mA/cm2Anodizing for 20-120 min to form an oxide film with a thickness of 5-50 μm on the surface of the titanium and the titanium alloy;
2) soaking the titanium oxide film in 1-20 mol/L aqueous alkali at 30-80 ℃ for 5-48 hours to form a porous titanate gel layer with a net structure on the surface of the oxide film;
3) carrying out heat treatment on the materials at the temperature of 400-900 ℃ for 0.5-3 hours, heating along with a furnace, and cooling along withthe furnace to crystallize a titanate gel layer with a net structure, wherein the thickness of the titanate gel layer is 5-20 mu m;
4) and immersing the treated material into a human body bionic liquid for 1-30 days to form a Ca and P rich apatite layer close to the bone.
2. The method according to claim 1, wherein the alcohol solution in step 1) is methanol.
3. The method according to claim 1, wherein the nitrate-based electrolyte in step 1) is sodium nitrate.
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| CN100341587C (en) * | 2005-06-14 | 2007-10-10 | 河北工业大学 | Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method |
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| CN100430099C (en) * | 2005-12-23 | 2008-11-05 | 中国科学院金属研究所 | Bioactive coating on surface of Titanium or titanium alloy and its preparing method |
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| CN106163580B (en) * | 2014-03-24 | 2020-06-26 | 混合金属股份公司 | Method for manufacturing a porous metal material for biomedical applications and material obtained by said method |
| CN104911674A (en) * | 2015-06-30 | 2015-09-16 | 四川大学 | Bioactive coating on surface of porous metal material and preparation method of bioactive coating |
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